Mineral concentration



Patented'Mar. 31, 1942 MINERAL CONCENTRATION Ludwig Jacob Christmann, Yonkers, N. Y., and David Walker Jayne, Jr., Old Greenwich, and Stephen Edward Erickson, Springdale, Conn., assignors to American Cyanamid Company, New York, N. Y., a. corporation of Maine No Drawing.

Application- March 30, 1940,

Serial No. 326,952

11 Claims. 7 (Cl. 209-166) The present invention relates to mineral concentration. More particularly it relates to a new class of reagents for selectively separating acidic minerals from ore materials.

Still more particularly it relates to the use of the reaction products of polyalkylene polyamines with fatty acids or fatty acid glycerides or other esters and the substantially water soluble salts of such products, as promoters or collectors for acidic minerals in froth flotation, film flotation, Stratification, agglomeration, tabling, and related mineral separation processes. While the present invention is not limited to any particular ore concentrating process or to any particular ore, its most important field of usefulness is in connection with froth flotation processes of separating silica or silicate minerals, such as mica from non-metallic ores such as limestone, bauxite, barytes, ilmenite, calcite and the like, and especially phosphate minerals.

A recent development in processes for the concentration of ores is one in which the so-called cationic reagents" are used as promoters or collectors for acidic siliceous gangues to effect a separation from the ore values. The use of these cationic reagents has resulted in a more economical and efficient method of recovering the ore values from a number of ore materials and particularly in connection with phosphate bearing ores in which the siliceous gangue is floated away from the phosphate minerals.

In accordance with this invention natural ores or artificial materials comprising mixtures of acidic minerals with other mineral constituents are subjected to a separation or concentration process in the presence of a promoter for the acidic ore minerals, said promoter being the condensation products of polyalkylene polyamines and fatty acids or the salts of such products, to effect a separation of the acidic minerals from the other ore constituents.

The present invention relates to an entirely new class of promoting or collecting reagents for acidic minerals. These compounds are surface active compounds and are basic in character. These new reagents are promoters for negatively charged or acidic ore materials. The promoter action will of course, vary with different acidic ore materials and with the different polyalkylene polyamine fatty acid condensation products or salts used. In the past various theories have been advanced as to the manner in which some acidic siliceous promoters worked, one of which was that positively charged surface active ions erals, and hence they are sometimes loosely referred to in the art as cationic reagents.

We have found that it is not necessary to the present invention to use salts as similar results are obtained with the condensation products themselves, provided satisfactory dispersion and distribution is effected. The present invention is accordingly not intended to be limited in any way to the use of a silica promoter which is highly ionized. The interaction between the surface of the silica and the promoter does not appear to be tied up exclusively with the presence of actual ions. The theory advanced in the prior art does not therefore appearto be correct as applied to silica flotation, or at least it does not appear to be a necessary factor in the present, invention. We do not wish to ad- Vance any definite theory of action in silica flotation and the present invention is not intended to be limited to any particular theory of the socalled cationic reagent.

The compounds that have been found to have a selective filming attraction for acidic minerals and are useful in carrying out the present invention include broadly the reaction products of polyalkylene polyamines with fatty acids or fatty acid glycerides or other esters and salts of these reaction products. The general method of preparing the reagents employed in carrying out the present invention comprises heating a fatty acid, glyceride, or the likewith a polyalkylene polyamine at a temperature of from Bil-250 C. until the reaction is complete. -The products are usually homogeneous viscous pastes which combine with acids such as formic, acetic, hydrochloric and the like to yield salts which are soluble in water. These reaction products are those most probably represented by the following general formula: Y-CONHA-Z in whichA rep-.

resents the group CHR-CHRNH- and there are two or more such groups serially arranged, R-and R. may be hydrogen or alkyl, radical, Y stands for an aliphatic hydrocarbon radical containing at least nine carbon atoms which hydrocarbon radical may contain one or more double bonds and may be substituted by hydroxy groups, and Z stands for hydrogen or the 'acyl radical of an aliphatic fatty acid containing at least ten carbon atoms, and the acid salts of such compounds.

Representative polyalkylene 'polyamines which may be employed in condensing with the fatty acids are diethylenetriamine, dipropylene triamine, dibutylene triamine, triethylerie tetrahad a strong affinity for anionic or acidic minmine, tetraethylene pentamine, or mixtures of any two or more of such polyamines either as relatively pure compounds or crude mixtures. In general they are polyamines, the different amino groups of which are separated from one another by a hydrocarbon radical containing 7 from 2 to 12 carbon atoms. The polyalkylene polyamines may be prcduced by heating an alkylene chloride with ammonia under pressure at a temperature of about 80-120 C. When ethylene chloride is employed there is obtained a mixture of diethylene triamine, triethylene tetramine, tetraethylene pentamine, and also some ethylene diamine. The ethylene diamine can be removed from the mixture of the higher polyethylene polyamines by distillation. When propylene chloride, butylene chloride, amylene chloride, and the like, are employed instead of ethylene chloride, the corresponding polyalkylene polyamines are obtained. The expression polyalkylene polyamine employed in the claims therefore refers to and is intended to include any one of the polyamines referred to above or to a mixture of the above polyamines.

Either the saturated, unsaturated, or hydroxy fatty acids may be employed for reacting with the polyamines, the preferred ones being those having at least nine carbon atoms, for example, lauric, palmitic, stearic, oleic, ricinoleic, capric, myristic, mixtures of such acids and especially mixtures of the fatty acids obtained from the fats and oils of either vegetable or animal sources or their glycerides such as those in coconut'oil, palm oil, palm kernel oil, cotton seed oil, corn oil, linseed oil, olive oil, peanut oil, fish oils, and the like.

The compounds used in the present invention are not limited to those produced by reacting any particular molecular ratio of the polyalkylene polyamine to the fatty acid but preferably they are the mono-acidyl, or they may be crude mixtures which may contain an excess of either the polyallzylene polyamines or the fatty acid substances.

The reagents of the present invention are effective promoters or collecting agents for acidic ore materials generally and said acidic materials may be either worthless gangue or valuable ore constitutents. ever, is in connection with the froth flotation of silica from non-metallic ores in which the siliceous gangue may represent a minor proportion of the ore rather than metallic and sulfide ores in which the gangue usually represents the major Representative acidic oreproportion of the 'ore.

materials are the feldspars, quartz, pyroxenes,

the spinels, biotite, muscovite, clays, and the like.

While as stated heretofore the present invention is not limited to the treatment of any particular ore material, it has been found to be well suited for froth flotation of silica from phosphate rock, and this is the preferred embodiment of the 'invention. In the processes of removing silica from phosphate rock the conditions are such that practically complete removal of the silica must be accomplished in order to produce a salable phosphate material. It is therefore an advantage of this invention that our reagents not only effect satisfactory removal of the silica but are economical: in amounts used. The quantities required range from 1 pound to 2.0 pounds per ton of ore depending upon the particular ore'and the particular reagent. The invention is not, however, limited to the use of such quantities.

These reagents have also been successfully used The most important use, howfor the flotation of feldspar from quartz and for the flotation of mica from quartz and calcite.

The reagents of the present invention may be used alone or in mixtures with other promoters. They may likewise be used in conjunction with other cooperating materials such as conditioning reagents, activators, frothing reagents, depressing reagents, dispersing reagents, oily materials such as hydrocarbon oil fatty acids or fatty acid esters.

These new reagents are also adaptable for use in any of the ordinary concentrating processes such as film flotation, tabling, and particularly in froth flotation operations. The ore concentrating processes employed will depend upon the particular type or kind of ore which is being processed. For example, in connection with phosphate rock, relatively coarse, phosphate bearing material, for example 28 mesh and larger, can be economically concentrated by using these reagents in conjunction with other materials such as fuel oil or pine oil and subjecting to concentration by the use of tables or by fllm flotation. The -28 phosphate rock material is best concentrated by means of froth flotation employing these improved silica promoters.

When the reagents of the present invention are employed as promoters in the froth flotation of silica from phosphate rock, which is the preferred embodiment thereof, the conditions may be varied in accordance with procedures known to those skilled in the art. The reagent may be employed in the form of aqueous solutions, emulsions, mixtures, or solutions in organic solvents such as alcohol and the like. The reagents may be introduced into the ore pulp in the flotation cell without prior conditioning or they may be conditioned with the ore pulp prior to the actual concentration operation. They may also be stage fed into the flotation circuit.

Other-improved phosphate flotation features which are known may be utilized in connection with the present invention such as splitting the phosphate flotation feed into a plurality of size ranges and floating each size separately as described in the U. S. Patent No. 2,156,245, the very complete removal of the slime prior to flotation which is also an aid to better results as pointed out in the Erickson application Serial No. 325,011, filed March 20, 1940, and the Mead and Maust application Serial No. 320,121, flled February 21, 1940, which describes a process for classifying and desliming phosphate flotation feed by means of a hindered settling classifier and which desllmed feed is well suited for treatment in accordance with this invention.

The invention will 'be further illustrated by the following specific examples which are illustrations of the preferred embodiments thereof, but

. it is not intended to limit the invention thereby.

EXAMPLE 1 Flotation tests as follows were made on a sample of Florida phosphate ore from the Old Colony mine near Brewster. This ore material which was essentially --48 +200 mesh material was agitated and scrubbed" with water to break up the clay balls. The slimes were subsequently removed by decantation and washing repeated until the ore material was substantially free of pulp. Themachine was started up and the pulp and reagent mixed for five seconds. Air was then admitted to the machine and the resulting concentrate was skimmed off for three minutes.

the assay is less than about 5% insoluble) the phosphate product is of a better grade than is currently produced by the flotation of phosphate particles from the quartz.

The flotation test ,products were then filtered, 5 In all the tests the weight recovery of the dried, weighed and assayed. The metallurgical phosphate product is much higher than would data obtained in these tests are presented in be obtainedin the soap fiotation' of the phosphate Table I. particles. Likewise the waste product (quartz' TABLE I ("oncentrate Tailing 'lesl Feed. Lbs/ion No. insol. Y Dist UM Rmmnt tested feed (".eht lnscl. inSUL eight Insol. insoL Pen-en. Percent Percml Percent Percenf Prrrenl Il'rr'rnf 1 55. 63 60. 89 37. 00 95. 22 30.11 6.80 4. 7s Acetate of the reaction product of diethylene triaminc and 1.0

coconut oi 2 55. 70 61.62 86.40 95. 59 38.38 6.40 4.41 Acetate of thei reaction product of dicthylcnc triainine and 1.0

' myristi'c aci 3 55. 29 63. 11 84. 26 00. 17 36. 39 5. 74 3. 83 Acetate of the reaction product of 48 parts mixed polyethylene 1. 0

polyamines and 60 parts coconut oil. 4 55. 44 65. 37 S3. 07. 98 34. 63 3. 24 2.02 Acetate oi the reaction product of parts mixed polyethylene 1. 0

polyamines and 60 parts coconut oil. 5 55. 051 65. x3. 26 07. 94 34. 50 3. 32 2. 06 Acetate of the reaction product of 35 parts mixed polyethylene 1.0

. polyamines and parts coconut oil. 0 55. x4 61. 11 87. 40 95. 38. 89 6. 24 4. 35 Acetate 0f the reaction product of 30 parts mixed polyethylene 1. 0 polyamincs and 60 parts coconut oil. p 7 55. 13 68. 34 79. 44 98. 48 i 31. 66 2. 64 1. 52 Mixture of 80 parts of the reaction product of mixed polycthyl-. 0. 5

ene polyamincs and coconut oil, and 20 parts of coconut oil. Higheralcoholfrothelz 0.67

EXAMPLE 2 30 concentrate) is much higher in insoluble con- Another series of tests was run on different sample of phosphate rock from the Old Colony mine. The original sample used in these tests contained less slime than the sample used for the preceding tests. The testing procedure, scrubbing," desliming and flotation, used for this series of tests was the same as that followed in the previous tests. The metallurgical data obtained in these tests are found in Table II.

tents than is currently produced by the soap flotation process.

EXAMPLE 3 35 Tasr ON A SAMPLE RAKE SANDS FROM THE TAILING PRODUCED BY 'rirn VALLEY FORGE CEMENT COM- I'ANY TABLE II Concentrate 'lailing Test. Feed, Lbs ton No 111501. Y Dist Dist Rmsm" feed Vi eight Insol. insol- Vi eight Insol. ipsoh Percent Percent Percent Percent Percent Percent Percent 1..... 49. 57 58. 26 83.00 97.56 41. 74 2.90 2. 44 Acetate of reaction product mixed polyethylene polyamines 1.00

and coconut oil.

' o 0. 00 2. 50. 43 62.86 18. 40 91. 72 37.14 3.10 2. 28 {Pine on Q16 Acetate of reaction product mixed polyethylene polyamincs 1.00 3 50.14 63.67 77.00 97.78 36.33 3.08 2. 22 and coconut oil.

a Pine oil 0.16 Acetate of reaction product mixed polyethylene polyamines 0.70 4... 49.64 54.86 85.32 94. 29 45.14 6. 28 5.71 and fish oil.

' Pine oil 0. 16 V Acetate of reaction product mixed polyethylene polyam 0.60 5 49.34 65. 63 73.42 97.66 34.37 3.36 2.34 and palm kernel oil.

' Pine oil 0. l6 Acetate of reaction product mixed polyethylene poly mines .70 6. 49. 41 67. 27 71. 86 97.84 32. 73 3. 26 2. 16 and palm kernel oil. 1

Pine oil 0. 16 Acetate of reaction product mixed polyeth, .50 7. 49.89 59 i0 79. 82 94. 88 40. 6. 28 6. 12 and cottonseed 011.

g Pine oil 0. 10 Acetate of reaction product mixe .60 8 49. 73 63.74 75.26 96.47 36.26 4. 84 3.53 and cottonseed oils Pine oil- 0. 16 Reaction product of mixed polyethylene and 0000- 0. 80 9 50.07 60. 79 80.76 98.04 39.21 2.50 1.96 nut oil. I A

Higher alcohol frother 1. 07 Reaction product of mixed polye ylene poly mines and coeo- 0. 90 10 49.93 50. 81.00 97.65 40.25 2.92 2.35 nut 011.

Higher alcohol frother 1. 20 Mixture of 80 parts of the react oduct of mixed polyethy- 0. 70 11 40. 06 56. 30 85. 38 96. 33 43. 70 4. 20 3. 67 lene polyamines and coconut oilgand 20 parts of coconut oil.

Higher alcohol frothcr 0. 03

An analysis of the metallurgical data found in Tables I and II show that in all tests the phosphate product (tails) is of a satisfactory marketable grade. In many of the tests (those in which The rake classifier sands are treated by flotation to remove part of the alumina which is present in the form of mica.' The removal of silica is not desired. The rake sands were composed of calcite, mica, quartz, and pyrite. Analyses are given A charge of this material containing 600 grams of dry solids was placed in a. laboratory size Fagergren flotation machine and diluted to 22% solids with tap water.

1.0 lb. of AiC1a.6H2O per ton of rake sands was added to the charge and conditioned with the pulp for 1 minute. Then 0.15 lb. of the acetate oi the reaction product of mixed .polyethylene polyamines and coconut oil and 0.05! lb. of a a higher alcohol frother per ton of rake sands were added. The resulting concentrate was skimmed oi! for three minutes. The results of this test are given below:

Test III Distribution Weight fAizO: S10:

A120: SlOl Percent Percent Pcrrrnf (om-entmtv 221.28 l4.i 41.80 49.70 25. 'laiiing. 70.72 4.33 30.70 50.30 74. Food 100.00 0.00 37.91 100.00 100.

EXAMPLE 4 FLO'IA'IIUN or SILICA Fuoir AN Inox Out:

A sample of magnetic separation plant tailings was used in these tests. The screen analysis of this material is given below:

Mesh ('iylcr) Weight- Percent +65 0v 49 +100 1.59 +150 0. 22 +200 16. 39 +325 7. 12 325 68. i9

This material assayed about 23% Fe. It con sisted of magnetite, limonite and quartz. Flotacleaned by refloating. The results or this test are given below:

. Weight Fe Dist. Fe

- Per cent Per cent Per cent Slime i 12.81 13.43 7. 68 Clean concentrate. 38. 25 ll. 38 19.38 Clean tail. 28. 81 22. 80 29. 33 Rough tail. 20. i3 48. 67 43. 03 1o Feed 100.00 22. 40 100.00

tion of the iron minerals away from the quartz resulted in therecovery of the magnetite in a low grade concentrate. The limonite was not floated, however.

A test on the flotation of'the silica from the iron minerals was conducted, using a charge 01' the tailing deslimed at approximately 1000 mesh in respect to the settling rate of quartz. The deslimed material was placed in a Fagergren flotation machine and diluted with tap water. 0.50 lb. of the acetate of the reaction product of mixed polyethylene polyamines and coconut oil and 0.057 1b. of a higher alcohol frother per ton of tailing were then added and conditioned with the pulp for 3 seconds. 'Air was admitted and the resulting rougher concentrate was skimmed ofi for 2 minutes. This rougher concentrate was- The rougher tailing resulting from the flotation of the silica contained both magnetite and limonite and assayed nearly twice as high in iron as any concentrate that was produced by conventional soap-flotation of the iron minerals.

We claim:

1. In ore concentrating processes of separating acidic ore materials from non-metallic ore constituents the process which comprises carrying out the concentration operation in the presence of a promoter for the acidicore material, said promoter being chosen from the,group consist-' ing of the reaction products of polyalkylene polyamines, represented by the following general formula:

ii I! in which n, m, and :c aresmall whole numbers with higher fatty acids or esters and acid addition salts thereof, said compounds being free from sulionic groups.

2. In ore concentrating processes .of separating acidic siliceous gangue from non-metallic ore constituents the process which comprises carrying out the concentrating operation in the presence of a collector for the acidic siliceous gangue said collector comprising at least one of the compounds represented by the following general formula: Y-CONH-AZ in which A represents the group CHR-CHR'-NH and there are two or more such groups serially arranged. R and R are members of the group consisting of hydrogen and alkyl radicals, Y stands for an aliphatic hydrocarbon radical containing at least nine carbon atoms which hydrocarbon radical may contain one or more double bonds and may be substituted by hydroxy groups, Z is a member of the group consisting of hydrogen and acyl radicals of an aliphatic fatty acid containing at least ten carbon atoms, and salts of such compounds, said compounds being free from suli'onic groups.

3. In ore concentrating processes of separating acidic siliceous ganguefrom phosphate ore values the process which comprises carrying out the concentrating operation in the presence of a collector for the acidic siliceous gflngue, Said collector comprising at least one of the com pounds represented by the following general formula: Y--CO-NHAZ in which A represents the group CHR-CHRJ-NH and there are two or more such groups serially arranged, R and R are members of the group consisting of hydrogen and alkyl radicals, Y stands for an allphatic hydrocarbon radical containing at least nine carbon atoms which hydrocarbon radical may contain one or more double bonds and may be substituted by hydroxy groups, Z is a, member of the group consisting of hydrogen and acyl radicals of an aliphatic fatty acid containing at least ten carbon atoms, and salts of such comphosphaie pounds, said compounds being free from sulfonic groups.

4. In the froth flotation process of separating non-metallic ore values from acidic siliceous gangue, the step which comprises subjecting the ore to froth flotation in the presence of a reagent chosen from the group consisting of the reaction product of polyalkylene polyamines, represented by the following general formula:

in which n, m, and :c are small whole numbers with a fatty acid having at least ten carbon atoms or esters of such fatty acids, and the acid addition salts of such reaction products, said compounds being free from sulfonic groups.

5. In the froth flotation process of separating phosphate ore values from acidic siliceous gangue, the step which comprises subjecting the ore to froth flotation in the presence of a reagent chosen from the groups consisting of the reaction products of polyalkylene polyamines, represented by the following general formula:

.1: are small whole numbers having at least ten carbon atoms or esters of such fatty acids and the acid addition salts of such reaction products, said compound bein free from sulfonic groups.

6. In the froth flotation process of separating ore values from acidic siliceous gangue, the step which comprises subjecting the ore to froth flotation in the presence of a reagent chosen from the groups consisting of the reaction products of polyalkylene polyamines, represented by the following general formula:

H II

in which n, m, and a: are small whole numbers with coconut oil fatty acids or esters of such fatty acids, and the acid addition salts of such reaction products, said compounds being free from sulfonic groups.

'7. In the froth flotation process of separating phosphate ore values from acidic siliceous gangue, the step which comprises subjecting the ore to froth flotation in the presence of a reagent chosen from the groups consisting of the reaction products of polyalkylene polyamines, repin which n, m, and with a fatty acid resented by the following general formula:

N(C,.Hz- 1- m 2nN\ n n n in which n, m, and a: are small whole numbers with palm kernel oil fatty acid or esters of such fatty acids and the acid addition salts of such reaction products, said compounds being free from sulfonic groups.

8. In the froth flotation process of separating phosphate ore values phosphate ore values from acidic siliceous gangue, the step which comprises subjecting the ore to froth flotation in the presence of a reagent chosen from the groups consisting of the reaction products of p lyalkylene polyamines, represented by the following general formula:

in which n, m, and a: are small whole numbers with myristic acid or esters of such fatty acids, and the acid addition salts of such reaction products, said compounds being free from sulfonic groups.

9. In the froth flotation process of separating from acidic siliceous gangue, the step which comprises subjecting the ore to froth flotation in the presence of a reagent chosen from the groups consisting of the reaction products of mixed polyethylene polyamines, represented by the following general formula.

in which a: is a small whole number with coconut oil fatty acid or esters of such fatty acids, and the acid addition salts of such reaction products, said compounds being free from suifonic groups.

10. In the froth flotation process of separating phosphate ore values from acidic siliceous gangue, the step which comprises subjecting the ore to froth flotation in the presence of a reagent chosen from the groups consisting of the reaction products of mixed polyethylene polyamines, represented by the following general H H H in which a: is a small whole number with myristic acid or esters of such fatty acids, and the acid addition salts or such reaction products, said compounds being free from sulfonic groups.

LUDWIG JACOB CHRISTMANN. DAVID WALKER JAYNE, JR. STEPHEN EDWARD ERICKSON.

-CER1IFICATE 0F commcnon. 4 men 51, 1912. mm JACOB cnxxsmn, ET AL.

Patent 11 0. 2,278,060.

it is hereby certified that error appears in the printed specification of the above numbered patent requiring correction follows: Page 5, first column, line 514., for "compound" read -cempounda--; and second column, line k7, claim 10 after"'products" and before the period insert the commend words eaid compound: being free from sulfonic groups; and that the eejid Letters Patent should be read with this correction thereinthet the ememny conform to the record of the case in the Patent Office. Signed and sealed this 26th day of m A. 1). 191m;

Henry Van Arsdale, (Seal) Acting commiesioner of Patents. 

